Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

Bulletin of the Korean chemical society

Dae Won Cho¹  Sun Wha Oh¹  Jin Ying Xue¹  Hea Jung Park¹  Ung Chan Yoon¹  Dong Uk Kim¹  Patrick S Mariano¹ 

关键词: Single electron transfer;    Photochemistry;    N-[(Trimethylsilyl)alkyl]saccharin;    Silyl transfer;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature . Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and �?-hydrogen abstraction pathways.

【 授权许可】

Unknown